JPS582063B2 - Manufacturing method for thermosetting polyurethane molded products - Google Patents
Manufacturing method for thermosetting polyurethane molded productsInfo
- Publication number
- JPS582063B2 JPS582063B2 JP55070860A JP7086080A JPS582063B2 JP S582063 B2 JPS582063 B2 JP S582063B2 JP 55070860 A JP55070860 A JP 55070860A JP 7086080 A JP7086080 A JP 7086080A JP S582063 B2 JPS582063 B2 JP S582063B2
- Authority
- JP
- Japan
- Prior art keywords
- isocyanate
- parts
- thermoplastic
- resin
- various
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/708—Isocyanates or isothiocyanates containing non-reactive high-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
【発明の詳細な説明】
本発明は熱硬化性ポリウレタン成形品の製造法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing thermosetting polyurethane molded articles.
熱可塑性ポリウレタンエラストマーは他のエジストマー
と比較して硬度が高い、それにも拘らず高い弾性率、引
張り強さ、耐油性を具備するため、この特長を利用した
巾広い用途がある。Thermoplastic polyurethane elastomers have high hardness compared to other elastomers, but they also have high elastic modulus, tensile strength, and oil resistance, so they have a wide range of uses that take advantage of these characteristics.
しかしながら熱可塑性ポリウレタンエラストマーは本質
的に線状構造であるため極性溶剤に溶解してしまう。However, since thermoplastic polyurethane elastomers have an essentially linear structure, they dissolve in polar solvents.
又、連続的な繰返し摩耗に対しては熱蓄積が大きいため
摩擦接触部分が熱溶融してしまう欠点があった。In addition, there is a drawback that the frictional contact portions are melted due to large heat accumulation due to continuous repeated wear.
上記の欠点を補うこめにポリウレタンエラストマーの分
子内に架橋構造を持たすとよろことは従来から知られて
いる。It has been known for some time that polyurethane elastomers may have a crosslinked structure in their molecules in order to compensate for the above drawbacks.
そして高品位の架橋したポリウレタンエラストマーに転
化させる方法としては例えば、次に記述する方法が知ら
れている。For example, the following method is known as a method for converting into a high-quality crosslinked polyurethane elastomer.
１）注型成形法に見られる様に水酸基を有する線状のポ
リエステル又はポリエーテルから、該ポリエステル又は
ポリエーテルを、該水酸基との反応のために必要な量よ
りも過剰の有機ジインシアネートと反応させることによ
って、架橋したポリウレタンエラストマーを製造する方
法。1) From a linear polyester or polyether having hydroxyl groups, as seen in the cast molding method, the polyester or polyether is reacted with an organic diincyanate in excess of the amount necessary for reaction with the hydroxyl groups. A method of producing a crosslinked polyurethane elastomer by.
２）溶液に溶解された本質的に線状のポリウレタンを、
溶剤に溶解された３〜４宮能末端ＮＣＯを有する架橋剤
を混合せしめ、離型紙上にコーティング又は織布等にデ
イピイング後乾燥機にて溶剤を揮散することによって、
架橋したポリウレタンエラストマーを製造する方法。2) an essentially linear polyurethane dissolved in a solution;
By mixing a crosslinking agent having 3-4 function terminal NCO dissolved in a solvent, coating it on a release paper or dipping it on a woven fabric, etc., and then volatilizing the solvent in a dryer.
A method of producing a crosslinked polyurethane elastomer.
前記１）の製造法は長い経験と熟練とによる高度な技術
を必要とし、押出し加工の如く電線、チューブ等の連続
成形には不向きである。The production method 1) requires advanced technology based on long experience and skill, and is not suitable for continuous molding of electric wires, tubes, etc., such as extrusion processing.
又、２）は溶剤を含有しているためコーティング方法以
外で作成される小型成形品には不向きであった。In addition, since method 2) contains a solvent, it is not suitable for small molded products made by methods other than coating methods.
本発明者等は前記従来の架橋したポリウレタンエラスト
マ一の欠点を改良すべく種々研究を重ねた結果、末端に
２個以上のイソシアネート基を持つ化合物を、前記イソ
シアネート基と反応を起さず、水吸収性が殆んどなく、
更に熱可塑性ポリウレタンと相溶性を有する熱可塑性樹
脂と混和し、得られた混和物を熱可塑性ポリウレタン樹
脂に配合し、次いでこの混和物を押出成形機、射出成形
機およびミキシングロール等で溶融混練せしめ、混練中
に、熱可塑性ポリウレタン樹脂中に存在すル水酸基、ア
ミン基又はウレタン結合、ウレア結合等とイソシアネー
ト基との反応により架橋を生成せしめて、熱硬化性ポリ
ウレタン成形物が得られることを知見し、本発明を完成
するに至った。The present inventors have conducted various studies to improve the shortcomings of the conventional crosslinked polyurethane elastomer, and as a result, they have developed a compound having two or more isocyanate groups at the end, which does not react with the isocyanate groups, Almost no absorption
Furthermore, it is mixed with a thermoplastic resin that is compatible with the thermoplastic polyurethane, the resulting mixture is blended with the thermoplastic polyurethane resin, and then this mixture is melt-kneaded using an extrusion molding machine, an injection molding machine, a mixing roll, etc. It was discovered that during kneading, a thermosetting polyurethane molded product can be obtained by generating crosslinks through the reaction of isocyanate groups with hydroxyl groups, amine groups, urethane bonds, urea bonds, etc. present in thermoplastic polyurethane resins. However, the present invention was completed.
本発明においては熱可塑性ポリウレタン樹脂中のウレタ
ン結合のＨ原子とインシアネート基とによるアロファネ
ート結合又はウレア結合のＨ原子とイソシアネート基と
によるピューレット結合の形成により、架橋をもたらす
ものであるが、この結合の利用は例えば西ドイツ特許第
８３１７７２号、特開昭４７−２０２９３号公報にも記
載されているが、上記引用特許においては、まず混合時
に第１段階としてウレタン基を介する連鎖生長、第２段
階としそウレタン基のＨ原子とアロファネートを形成し
、分子内の架橋に寄与する、このような手段によると熱
可塑性ポリウレタン樹脂を押出成形や射出成形に応用す
ることは通常の処方においては不可能に近い。In the present invention, crosslinking is brought about by forming an allophanate bond between the H atom of a urethane bond and an incyanate group in the thermoplastic polyurethane resin, or a puree bond between an H atom of a urea bond and an isocyanate group. The use of bonding is also described in, for example, West German Patent No. 831,772 and Japanese Patent Application Laid-Open No. 47-20293, but in the above cited patents, the first step during mixing is chain growth via urethane groups, and the second step is Toshio forms an allophanate with the H atom of the urethane group and contributes to intramolecular crosslinking. Using this method, it is impossible to apply thermoplastic polyurethane resin to extrusion molding or injection molding using normal formulations. close.
本発明においては熱可塑性ポリウレタン樹脂にイソシア
ネートバッチを配合し、この配合物を押出成形機や射出
成形機に供して成形することにより簡単に熱硬化性ポリ
ウレタン成形品を得ることができる。In the present invention, a thermosetting polyurethane molded article can be easily obtained by blending an isocyanate batch with a thermoplastic polyurethane resin and molding this blend using an extrusion molding machine or an injection molding machine.
前記のインシアネートバッチとは末端に２個以上のイン
シアネート基を持つ化合物を、前記イソシアネート基と
は反応を起さず、吸水性が殆んどなくかつ熱可塑性ポリ
ウレタン樹脂との相溶性が良好な熱可塑性樹脂でバッチ
化したものである。The above-mentioned incyanate batch is a compound having two or more incyanate groups at the end, which does not react with the isocyanate groups, has almost no water absorption, and has good compatibility with thermoplastic polyurethane resin. It is made into a batch of thermoplastic resin.
イソシアネート基を持つ化合物をバッチ化するのに適し
た熱可塑性樹脂の具体例としては例えば、ポリ塩化ビニ
ル樹脂、ポリスチレン樹脂、アクリル樹脂、ＡＢＳ樹脂
、エステルゴム、ポリエチレンテレフタレート、ポリエ
チレン、ポリプロピレン、ポリアセタール、ポリカーボ
ネート、ニフッ化樹脂、四フツ化樹脂等が挙げられる。Specific examples of thermoplastic resins suitable for batching compounds having isocyanate groups include polyvinyl chloride resin, polystyrene resin, acrylic resin, ABS resin, ester rubber, polyethylene terephthalate, polyethylene, polypropylene, polyacetal, and polycarbonate. , difluoride resin, tetrafluoride resin, and the like.
また末端に２個以上のインシアネート基を持つ化合物の
具体例としては、
例えばジイソシアネートとして、２，４−トリレンジイ
ソシアネート、２，６−トリレンジイソシアネート及び
この両者の混合物、４，４′ジフエニルメタンジイソシ
アネート、ｍ−フエニレンジイソシアネート、４，４′
−ビフエニルイソシアネートなどの芳香族ジイソシアネ
ート及びテトラメチレンジイソシアネート、ヘキサメチ
レンジイソシアネート、オクタメチレンジイソシアネー
トなどの脂肪族ジイソシアネート、或いはキシレンジイ
ソシアネートなどの芳香族等、トリイソシアネートとし
て４，４’，４″−トリフエニルメタントリイソシアネ
ート、２， ４． ４’ビフエニルトリイソシアネ
ート、２，４，４′−ジフエニルメタントリイソシアネ
ートなどがある。Further, specific examples of compounds having two or more incyanate groups at the terminal include, for example, diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of both, 4,4' diphenyl Methane diisocyanate, m-phenylene diisocyanate, 4,4'
- Aromatic diisocyanates such as biphenyl isocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, or aromatic diisocyanates such as xylene diisocyanate, and 4,4',4''-triphenylmethane as a triisocyanate. Examples include triisocyanate, 2,4.4'-biphenyl triisocyanate, and 2,4,4'-diphenylmethane triisocyanate.
その他使用出来るイソシアネートとしてはこれらのジ又
はトリイソシアネートとジオール又はトリオールの様な
分子中に２個以上のヒドロキシル基をもつ化合物と反応
せしめ、反応生成物中に、なお２個以上のイソシアネー
ト基を有する付加生成物、或いはイソシアネート重合体
化合物等がある。Other isocyanates that can be used include reacting these di- or triisocyanates with a compound having two or more hydroxyl groups in the molecule, such as a diol or triol, so that the reaction product still has two or more isocyanate groups. These include addition products and isocyanate polymer compounds.
そして前記末端に２個以上のイソシアネート基を持つ化
合物を熱可塑性樹脂に混和するには、熱可塑性樹脂１０
０重量部に対してイソシアネート化合物を５〜１００重
量部の範囲で配合し、この配合物を温度１３０〜２５０
のミキシングロール又はバンバリーミキサーで充分に混
練して、冷却後粉砕機で粉砕してインシアネートバッチ
とする。In order to mix the compound having two or more isocyanate groups at the terminal with the thermoplastic resin, the thermoplastic resin 10
0 parts by weight, an isocyanate compound is blended in the range of 5 to 100 parts by weight, and this blend is heated at a temperature of 130 to 250 parts by weight.
The mixture is sufficiently kneaded using a mixing roll or a Banbury mixer, cooled, and then ground using a grinder to obtain an incyanate batch.
イソシアネート化合物を熱可塑性樹脂でバッチ化せずに
そのま寸熱可塑性ポリウレタンに添加すると、互いの融
点の差、溶融粘度の差から押出機、射出成形機のシリン
ダー内でスベリの現象が起き定量的な充分な混合は困難
である。If an isocyanate compound is added directly to thermoplastic polyurethane without batching it with thermoplastic resin, a phenomenon of slippage may occur in the cylinder of an extruder or injection molding machine due to the difference in melting point and melt viscosity. sufficient mixing is difficult.
ロール加工の場合にも、互いの融点の差、溶融粘度の差
からロール面でのスベリの現象が起き充分な混練が困難
である。Even in the case of roll processing, sufficient kneading is difficult due to the phenomenon of slippage on the roll surface due to the difference in melting point and melt viscosity.
本発明の方法によれば常温で固形のイソシアネートはも
ちろんこのこと、液状のイソシアネートも使用可能であ
る。According to the method of the present invention, not only isocyanates that are solid at room temperature but also liquid isocyanates can be used.
前記のイソシアネートバッチを熱可塑性ポリウレタン樹
脂に添加する場合、イソシアネートバツチのＮＣＯ％と
熱可塑性ポリウレタン樹脂のＮＣＯ％のトータルＮＣＯ
％が０．１〜１０％となる様に調整する。When the above-mentioned isocyanate batch is added to a thermoplastic polyurethane resin, the total NCO of the isocyanate batch NCO% and the NCO% of the thermoplastic polyurethane resin
Adjust so that the percentage is 0.1 to 10%.
イソシアネートバッチの添加量が少なすぎると架橋効果
が充分に起きず、又多すぎると未反応ＮＣＯが成形物に
着出現象を付与するので好ましくない。If the amount of the isocyanate batch added is too small, the crosslinking effect will not be sufficiently produced, and if it is too large, unreacted NCO will cause a depositing phenomenon on the molded product, which is not preferable.
本発明に於てイソシアネートバッチを熱可塑性ポリウレ
タン樹脂に添加して成形機により成形して熱硬化性ポリ
ウレタン成形品を得るときには、通常ペレット又はビー
ズ状の熱可塑性ポリウレタン樹脂を使用し、これにイソ
シアネートバツチを添加してタンブラーでよくタンブリ
ングした後成形機例えば射出成形機、押出成形機および
ロール等で目的とする成形品を得ることができる。In the present invention, when adding an isocyanate batch to a thermoplastic polyurethane resin and molding it with a molding machine to obtain a thermosetting polyurethane molded product, a thermoplastic polyurethane resin in the form of pellets or beads is usually used, and an isocyanate batch is added to the thermoplastic polyurethane resin. After the mixture is thoroughly tumbled in a tumbler, the desired molded product can be obtained using a molding machine such as an injection molding machine, an extrusion molding machine, a roll molding machine, or the like.
その時の成形温度は使用する熱可塑性ポリウレタン樹脂
によって相違するが、通常１２０〜２１０℃の範囲で行
なわれる。The molding temperature at this time varies depending on the thermoplastic polyurethane resin used, but is usually carried out in the range of 120 to 210°C.
本発明によって得られた成形品は成形直後は架橋反応が
充分に進んでいないため柔軟性があるが、成形後更に１
００℃で２時間熟成することにより架橋反応が完結し、
熱変形の少ない耐溶性のある成形物が得られる。The molded product obtained by the present invention is flexible immediately after molding because the crosslinking reaction has not progressed sufficiently, but after molding it is further
The crosslinking reaction was completed by aging at 00°C for 2 hours.
A melt-resistant molded product with little thermal deformation can be obtained.
本発明の製造法によると射出成形法の利点である小型成
形品の量産に適し、製品成形時に原料ロスが少なく、複
雑な形状の製品でも成形が容易であり、また押出成形に
よると成形品は連続した形状で得られ、使用するダイの
形状により無空、中空の一定断面をもつ連続成形品が得
られ各種の押出成形品が極めて容易に製造することがで
きる利点がある。The manufacturing method of the present invention is suitable for the mass production of small molded products, which is an advantage of the injection molding method, there is less raw material loss during product molding, and it is easy to mold even products with complex shapes. It has the advantage that it can be obtained in a continuous shape, and that a continuous molded product with a constant cross section that is empty or hollow can be obtained depending on the shape of the die used, and that various extrusion molded products can be produced extremely easily.
本法を利用して得られる成形品の例としては、射出成形
法によるボールジョイント類、各種プッシュ、各種ダス
トカバー、各種ショックアブソーバー、ブレーキストッ
パー類、Ｏ−リング類、給油リング類、板バネのスペー
サー、ドアロックストライカー、各種ギアー類 パッキ
ン類、シール材、プレート材、ピッカー、ＫＰホルダー
、ウレタンボール類、各種キャスター類、スラストワッ
シャー、チューナ一部品、水道栓、各種スポーツシュー
ズの靴底材、各種リフト、ヒールトップ類、スキーのグ
リップ材、スノーモービル用スプロケット、キャタビラ
ー類、軍靴及び安全靴等の靴底材、ゴルフボール、ベル
ト類、ガスケット、プラグ類、ソケット類など、又、押
出成形法による各種コンベアベルト類、水容器、醸造用
容器、フレキシブルコンテナー類、モーター油用・煮沸
用小袋、粉粒体の輸送用シート、各種カッパ類、衣類、
各種テープ類の如きフイルム押出加工物、インフレーシ
ョン加工物や、各種チューブ類、各種ホース類の如きチ
ューブ押出加工物や、地下ケーブル、海底ケーブル、電
力・通信ケーブル類、リード線、コンピューター配線、
自動車配線、各種エナメル線までの被覆押出加工物や、
各種ベルト類のベルト押出加工物等がある。Examples of molded products obtained using this method include injection molded ball joints, various pushers, various dust covers, various shock absorbers, brake stoppers, O-rings, oil supply rings, and leaf springs. Spacers, door lock strikers, various gears, packings, sealing materials, plate materials, pickers, KP holders, urethane balls, various casters, thrust washers, tuner parts, water faucets, sole materials for various sports shoes, various Lifts, heel tops, ski grip materials, sprockets for snowmobiles, caterpillars, sole materials for military boots and safety shoes, golf balls, belts, gaskets, plugs, sockets, etc., and also by extrusion molding. Various conveyor belts, water containers, brewing containers, flexible containers, motor oil and boiling bags, sheets for transporting powder and granules, various raincoats, clothing,
Film extrusion products such as various tapes, inflation products, tube extrusion products such as various tubes and hoses, underground cables, submarine cables, power/communication cables, lead wires, computer wiring,
Covered extrusion products such as automobile wiring and various enameled wires,
There are belt extrusion processed products of various belts.
又、ロール加工としては各種パック類、パッケージ類、
各種ラミネート品類、各種カッパ類、農業用ハウス、各
種ベルト類、合成皮革、フレキシブルコンテナー類の如
きカレンダー加工物や、各種パッケージ類、パック類等
の中空成形物が掲げられる。In addition, roll processing includes various packs, packages,
Various laminate products, various raincoats, agricultural greenhouses, various belts, synthetic leather, calendered products such as flexible containers, and hollow molded products such as various packages and packs are listed.
以下、実施例を示す。Examples are shown below.
実施例中、部は重量部である。In the examples, parts are parts by weight.
実施例 １
予め乾燥して水分を除去した軟質塩化ビニル樹脂ペレッ
ト（可塑剤ＤＯＰ５０ＰＨＲ）１００部にナフチレン−
１．５−ジイソシアネート２０部を加え、１５０〜１５
５℃のミキシングロールにて５〜１０分間混練する。Example 1 Naphthylene-
1. Add 20 parts of 5-diisocyanate, 150-15
Knead for 5 to 10 minutes using a mixing roll at 5°C.
混線物をロールから取りはずし冷却後粉砕機で粉砕して
フレーク状のイソシアネートバッチを得る。The mixed material is removed from the roll, cooled, and then ground in a grinder to obtain a flaky isocyanate batch.
次いで、このイソシアネートパッチ３０部を、予め乾燥
してある熱可塑性アジペート系ポリエステルポリウレタ
ンペレット１００部に配合し、タンブラーで充分混合し
た後、混合物をベント式押出機に供して１６０〜１８０
℃の温度で押出してストランドを得た。Next, 30 parts of this isocyanate patch was blended with 100 parts of previously dried thermoplastic adipate-based polyester polyurethane pellets, and after thorough mixing in a tumbler, the mixture was sent to a vented extruder to
Strands were obtained by extrusion at a temperature of °C.
得られたストランドは更に１００℃の温度で２時間熟成
を行なった。The obtained strand was further aged at a temperature of 100°C for 2 hours.
得られたストランドの物性値を測定した結果を第１表に
示す。Table 1 shows the results of measuring the physical properties of the obtained strands.
なお比較例として熱可塑性アジペート系ポリエステルウ
レタンのみを使用し、他は同一の条件でストランドを得
て、その物性値を測定した結果を第１表に示す。As a comparative example, strands were obtained using only thermoplastic adipate polyester urethane under the same conditions, and the physical properties of the strands were measured. Table 1 shows the results.
実施例 ２
了め乾燥して水分を除去した軟質塩化ビニル樹脂ペレッ
ト（可塑剤ＤＯＰ５０ＰＨＲ）１００部にヘキサメチレ
ンジイソシアネート三量化物４０部を加え、１５０〜１
５５℃のミキシングロールにて５〜１０分間混練する。Example 2 40 parts of hexamethylene diisocyanate trimer was added to 100 parts of soft vinyl chloride resin pellets (plasticizer DOP50PHR) that had been dried and water removed, and 150 to 1
Knead for 5 to 10 minutes using a mixing roll at 55°C.
混練物をロールから取りはずし冷却後、粉砕機で粉砕し
てフレーク状のイソシアネートバッチを得る。The kneaded material is removed from the roll, cooled, and then ground in a grinder to obtain a flaky isocyanate batch.
次いで、このイソシアネートバッチ１５部を、予め乾燥
してある熱可塑計アジペート系ポリエステルポリウレタ
ンペレット１００部に配合し、タンブラーで充分混合し
た後、混合物をベント式押出機に供して１６０〜１８０
℃の温度で押出してストランドを得た。Next, 15 parts of this isocyanate batch was blended with 100 parts of pre-dried thermoplastic adipate polyester polyurethane pellets, and after thorough mixing in a tumbler, the mixture was passed through a vented extruder to give a
Strands were obtained by extrusion at a temperature of °C.
得られたストランドは更に１００℃の温度で２時間熟成
を行なった。The obtained strand was further aged at a temperature of 100°C for 2 hours.
得られたストランドの物性値を測定した結果を第２表に
示す。Table 2 shows the results of measuring the physical properties of the obtained strands.
なお比較例として憎可塑性アジペート系ポリエステルポ
リウレタンのみを使用し、他は同一の条件でストランド
を得て、その物性値を測定した結果を第２表に示す。As a comparative example, a strand was obtained under the same conditions except that only a plastic adipate polyester polyurethane was used, and the physical properties of the strand were measured.Table 2 shows the results.
実施例 ３
予め乾燥して水分を除去した軟質塩化ビニル樹脂ペレッ
ト（可塑剤ＤＯＰ４０ＰＨＲ）１００部に４，４′ジフ
エニヌメタンジイソシアナート３０部を加え、１５０〜
１５５℃のミキシングロールにて５〜１０分間混練する
。Example 3 30 parts of 4,4' diphenymethane diisocyanate was added to 100 parts of soft vinyl chloride resin pellets (plasticizer DOP40PHR) that had been dried in advance to remove moisture, and 150 to
Knead for 5 to 10 minutes using a mixing roll at 155°C.
混練物をロールから取りはずし冷却後粉砕機で粉砕して
フレーク状のイソシアナートバッチを得る。The kneaded product is removed from the roll, cooled, and then ground in a grinder to obtain a flaky isocyanate batch.
次いでこのイソシアナートバッチ２０部を予め乾燥して
ある熱可塑性アジペート系ポリエステルポリウレタンペ
レット１００部に配合し、タンブラーで充分に混合した
後、混合物をベント式押出機に供して１６０〜１８０℃
の温度で押してストランドを得た。Next, 20 parts of this isocyanate batch was blended with 100 parts of pre-dried thermoplastic adipate polyester polyurethane pellets, and after thorough mixing in a tumbler, the mixture was sent to a vented extruder and heated to 160 to 180°C.
The strands were obtained by pressing at a temperature of .
得られたストランドは更に１００℃の温度で２時間熟成
を行なった。The obtained strand was further aged at a temperature of 100°C for 2 hours.
得られたストランドの物性値を測定した結果を第３表に
示す。Table 3 shows the results of measuring the physical properties of the obtained strands.
なお比較例として熱可塑性アジペート系ポリエステルポ
リウレタンのみを使用し、他は同一の条件でストランド
を得て、その物性値を測定した結果を第３表に示す。As a comparative example, strands were obtained using only thermoplastic adipate polyester polyurethane under the same conditions, and the physical properties of the strands were measured. Table 3 shows the results.
実施例 ４
予め乾燥して水分を除去したボリスチレン樹脂（スタイ
ロン４１０；旭ダウケミカル（株））７０部にナフチレ
ン−１．５−ジイソシアナート３０部を加え、１８０〜
１９０℃のバンバリーミキサーにて５〜７分間混練する
。Example 4 30 parts of naphthylene-1.5-diisocyanate was added to 70 parts of polystyrene resin (Styron 410; Asahi Dow Chemical Co., Ltd.) which had been dried in advance to remove moisture, and 180~
Knead for 5 to 7 minutes in a Banbury mixer at 190°C.
混和物をバンバリーミキサーから取りはずし冷却後粉砕
機で粉砕してフレーク状のイソシアナートバツチを得る
。The mixture is removed from the Banbury mixer, cooled, and then ground in a grinder to obtain flaky isocyanate batches.
次いでこのイソシアナートバッチ２０部を予め乾燥して
あル熱可塑性アジペート系ポリエステルポリウレタンペ
レット１００部に配合し、タンブラーで充分に混合した
後、混合物をベント式押出機に供して１６０〜１８０℃
の温度で押出してストランドを得た。Next, 20 parts of this isocyanate batch was previously dried and blended with 100 parts of thermoplastic adipate-based polyester polyurethane pellets, and after thorough mixing in a tumbler, the mixture was sent to a vented extruder and heated to 160-180°C.
A strand was obtained by extrusion at a temperature of .
得られたストランドは更に１００℃の温度で２時間熟成
を行なった。The obtained strand was further aged at a temperature of 100°C for 2 hours.
得られたストランドの物性値を測定した結果を第４表に
示す。Table 4 shows the results of measuring the physical properties of the obtained strands.
なを比較例として熱可塑性アジペート系ポリエステルポ
リウレタンのみを使用し、他は同一の条件でストランド
を得て、その物性値を測定した結果を第４表に示す。As a comparative example, strands were obtained using only thermoplastic adipate polyester polyurethane under the same conditions, and the physical properties of the strands were measured. Table 4 shows the results.
実施例 ５
予め乾燥して水分を除去したＡＢＳ樹脂（タフレツクス
４７０；三菱モンサント化学（株）製）７０部にナフレ
チレン−１５−ジイソシアナート３０部を加え、１９０
〜２００℃のバンバリーミキサーにて５〜１０分間混練
する。Example 5 30 parts of naplethylene-15-diisocyanate was added to 70 parts of ABS resin (Toughflex 470; manufactured by Mitsubishi Monsanto Chemical Co., Ltd.) which had been dried in advance to remove moisture, and 190 parts of naplethylene-15-diisocyanate was added.
Knead for 5-10 minutes in a Banbury mixer at ~200°C.
混練物をバンバリーミキサーから取りはずし冷却後粉砕
機で粉砕してフレーク状のイソシアナートバッチを得る
。The kneaded material is removed from the Banbury mixer, cooled, and then ground in a grinder to obtain a flaky isocyanate batch.
以下、実施例４と同配合、同条件で得られた架橋ポリウ
レタンストランド及び比較例の物性値を測定した結果を
第５表に示す。Table 5 below shows the results of measuring the physical properties of the crosslinked polyurethane strands obtained under the same formulation and conditions as in Example 4 and the comparative example.
Claims (1)
、前記インシアネート基と反応を起さない熱可塑性樹脂
と混和し、得られた混和物を熱可塑性ポリウレタン樹脂
に配合し、次いでこの配合物を成形機に供して成形する
ことを特徴とする熱硬化性ポリウレタン成形品の製造法
。1. A compound having two or more isocyanate groups at the end is mixed with a thermoplastic resin that does not react with the incyanate groups, the resulting mixture is blended with a thermoplastic polyurethane resin, and then this blend is A method for producing a thermosetting polyurethane molded product, which comprises molding it using a molding machine.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55070860A JPS582063B2 (en) | 1980-05-29 | 1980-05-29 | Manufacturing method for thermosetting polyurethane molded products |
| US06/265,244 US4347338A (en) | 1980-05-29 | 1981-05-19 | Process for preparing thermosettable polyurethane which comprises blending a polyisocyanate with a first thermoplastic resin and then blending with a second thermoplastic resin which is a polyurethane |
| DE8181302269T DE3170256D1 (en) | 1980-05-29 | 1981-05-21 | Process for preparing thermosettable polyurethane product |
| EP81302269A EP0041347B1 (en) | 1980-05-29 | 1981-05-21 | Process for preparing thermosettable polyurethane product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55070860A JPS582063B2 (en) | 1980-05-29 | 1980-05-29 | Manufacturing method for thermosetting polyurethane molded products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56167430A JPS56167430A (en) | 1981-12-23 |
| JPS582063B2 true JPS582063B2 (en) | 1983-01-13 |
Family
ID=13443732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55070860A Expired JPS582063B2 (en) | 1980-05-29 | 1980-05-29 | Manufacturing method for thermosetting polyurethane molded products |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4347338A (en) |
| EP (1) | EP0041347B1 (en) |
| JP (1) | JPS582063B2 (en) |
| DE (1) | DE3170256D1 (en) |
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| US4048253A (en) * | 1972-12-27 | 1977-09-13 | Fuji Photo Film Co., Ltd. | Adhesive coatings from ether-type polyester, urethane elastomer, and polyisocyanate |
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- 1981-05-19 US US06/265,244 patent/US4347338A/en not_active Expired - Lifetime
- 1981-05-21 DE DE8181302269T patent/DE3170256D1/en not_active Expired
- 1981-05-21 EP EP81302269A patent/EP0041347B1/en not_active Expired
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| JP2013215610A (en) * | 2013-06-27 | 2013-10-24 | Dunlop Sports Co Ltd | Golf ball |
| US9682283B2 (en) | 2014-06-27 | 2017-06-20 | Bridgestone Sports Co., Ltd. | Golf ball and method of manufacture |
| US10137334B2 (en) | 2014-06-27 | 2018-11-27 | Bridgestone Sports Co., Ltd. | Golf ball manufacturing method |
| US10232227B2 (en) | 2014-06-27 | 2019-03-19 | Bridgestone Sports Co., Ltd. | Golf ball and method of manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0041347A3 (en) | 1982-08-04 |
| EP0041347A2 (en) | 1981-12-09 |
| JPS56167430A (en) | 1981-12-23 |
| EP0041347B1 (en) | 1985-05-02 |
| DE3170256D1 (en) | 1985-06-05 |
| US4347338A (en) | 1982-08-31 |
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